Fabian Dauzvardis,Nina Borodin,Philip H Gilmartin,Joel Rosenthal,Robert Michael O'Dea,Thomas Epps, III,Mary Watson
Recognizing the potential of polymer-to-polymer transformations for plastics valorization, a new electrochemical strategy for the decarboxylative functionalization of polyacrylates has been developed. In contrast to most electrochemical approaches to plastic waste valorization that use small-molecule mediators or only form deconstruction products, this report describes one of the first direct electrochemical redox upconversions of a commodity polymer and involves activation of poly(acrylic acid), a material commonly found in disposable diapers and other personal hygiene products. Via electrochemical decarboxylation, poly(acrylic acid) is converted to methyl ether-containing copolymers. Although methods to prepare the 1:1 regularly alternating poly(vinyl methyl ether-alt-maleic anhydride) are known, routes to generate copolymers with variable levels of vinyl methyl ether and acrylate moieties are unknown, but such polymers may have utility in similar applications, such as dentifrices. Tunable conversions with up to 62 mol% vinyl methyl ether content were achieved via controlled-current electrolyses at >100 mA. This approach enables efficient access to copolymers with broad range of comonomer content from a common waste polymer starting material.
{"title":"Tunable Conversion of Poly(Acrylic Acid) to Vinyl Methyl Ether Copolymers via Electrochemical Decarboxylation","authors":"Fabian Dauzvardis,Nina Borodin,Philip H Gilmartin,Joel Rosenthal,Robert Michael O'Dea,Thomas Epps, III,Mary Watson","doi":"10.1039/d6py00684a","DOIUrl":"https://doi.org/10.1039/d6py00684a","url":null,"abstract":"Recognizing the potential of polymer-to-polymer transformations for plastics valorization, a new electrochemical strategy for the decarboxylative functionalization of polyacrylates has been developed. In contrast to most electrochemical approaches to plastic waste valorization that use small-molecule mediators or only form deconstruction products, this report describes one of the first direct electrochemical redox upconversions of a commodity polymer and involves activation of poly(acrylic acid), a material commonly found in disposable diapers and other personal hygiene products. Via electrochemical decarboxylation, poly(acrylic acid) is converted to methyl ether-containing copolymers. Although methods to prepare the 1:1 regularly alternating poly(vinyl methyl ether-alt-maleic anhydride) are known, routes to generate copolymers with variable levels of vinyl methyl ether and acrylate moieties are unknown, but such polymers may have utility in similar applications, such as dentifrices. Tunable conversions with up to 62 mol% vinyl methyl ether content were achieved via controlled-current electrolyses at >100 mA. This approach enables efficient access to copolymers with broad range of comonomer content from a common waste polymer starting material.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"186 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuancheng Liu,John M. Tobin,Gary. S. Nichol,Dominic Taylor,Jiyao Huang,Carmen Rizzuto,Johannes C. Jansen,Alessio Fuoco,Neil B. McKeown
A novel monomer based on epoxydinaphthalene (EDN), a highly rigid bridged-bicyclic structural unit, was prepared using a high yielding reaction between 2,7-hydroxynaphthalene and the hydrate of 1,8-naphthalene dialdehyde. This monomer was used to make a poly(aryl ether ketone) and poly(aryl ether sulfone), EDN-PAEK and EDN-PAES, via efficient aryl ether bond formation, by reaction with cheaply available co-monomers. Both EDN-PAEK and EDN-PAES proved readily soluble in organic solvents allowing structural characterization and ready fabrication of robust self-standing films. Gas permeability measurements for He, H2, O2, N2, CO2 and CH4 indicated that these polymers provide a good trade-off between high selectivity and modest permeability relative to previously published data for structurally related polyketones or polysulfones.
{"title":"An epoxydinaphthalene monomer for the synthesis of a poly(aryl ether sulfone) and a poly(aryl ether ketone) with enhanced performance for membrane gas separations","authors":"Yuancheng Liu,John M. Tobin,Gary. S. Nichol,Dominic Taylor,Jiyao Huang,Carmen Rizzuto,Johannes C. Jansen,Alessio Fuoco,Neil B. McKeown","doi":"10.1039/d6py00312e","DOIUrl":"https://doi.org/10.1039/d6py00312e","url":null,"abstract":"A novel monomer based on epoxydinaphthalene (EDN), a highly rigid bridged-bicyclic structural unit, was prepared using a high yielding reaction between 2,7-hydroxynaphthalene and the hydrate of 1,8-naphthalene dialdehyde. This monomer was used to make a poly(aryl ether ketone) and poly(aryl ether sulfone), EDN-PAEK and EDN-PAES, via efficient aryl ether bond formation, by reaction with cheaply available co-monomers. Both EDN-PAEK and EDN-PAES proved readily soluble in organic solvents allowing structural characterization and ready fabrication of robust self-standing films. Gas permeability measurements for He, H2, O2, N2, CO2 and CH4 indicated that these polymers provide a good trade-off between high selectivity and modest permeability relative to previously published data for structurally related polyketones or polysulfones.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"486 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marta Castelnovo,Magdalena Janewska,Marleen Kamperman,Vincent S. D. Voet,Katja Loos,Dina Maniar
Petroleum-derived monomers have been extensively used in the manufacturing of thermoset polymers and composites because of their excellent thermomechanical performance. However, these materials rely on nonrenewable feedstocks and are typically nonrecyclable, which has raised significant environmental and sustainability concerns. As a result, increasing research efforts are being directed toward developing biobased alternatives that can reduce the dependence on nonrenewable feedstocks. Among these, furan-based monomers offer a promising alternative as raw materials for the production of a wide range of polymers and composites. Moreover, the development of covalent adaptable networks (CANs) and vitrimers from these molecules provides a viable solution for managing their end-of-life. This review provides an overview of recent advances in furan-derived thermosets, blends, composites, and vitrimers, with a particular focus on their thermomechanical properties, recyclability, and reprocessability, as well as the key parameters influencing these characteristics. On the basis of current findings, this review offers a perspective on the potential impact of furan-based polymers and their end-of-life strategies within the polymer industry.
{"title":"Progress in furan-derived thermosets, composites and covalent adaptable networks (CANs): an overview on thermomechanical properties and end-of-life","authors":"Marta Castelnovo,Magdalena Janewska,Marleen Kamperman,Vincent S. D. Voet,Katja Loos,Dina Maniar","doi":"10.1039/d6py00497k","DOIUrl":"https://doi.org/10.1039/d6py00497k","url":null,"abstract":"Petroleum-derived monomers have been extensively used in the manufacturing of thermoset polymers and composites because of their excellent thermomechanical performance. However, these materials rely on nonrenewable feedstocks and are typically nonrecyclable, which has raised significant environmental and sustainability concerns. As a result, increasing research efforts are being directed toward developing biobased alternatives that can reduce the dependence on nonrenewable feedstocks. Among these, furan-based monomers offer a promising alternative as raw materials for the production of a wide range of polymers and composites. Moreover, the development of covalent adaptable networks (CANs) and vitrimers from these molecules provides a viable solution for managing their end-of-life. This review provides an overview of recent advances in furan-derived thermosets, blends, composites, and vitrimers, with a particular focus on their thermomechanical properties, recyclability, and reprocessability, as well as the key parameters influencing these characteristics. On the basis of current findings, this review offers a perspective on the potential impact of furan-based polymers and their end-of-life strategies within the polymer industry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Among the well-established alkyne-based polymerization methodologies, the polymerization of activated-internal alkynes and phenols remains underdeveloped. Herein, a facile cesium carbonate catalyzed aldehyde-activated phenol-yne click polymerization was reported, and various regioregular poly(formyl ether)s (PFEs) with weight-average molecular weights up to 18 060 g mol−1 were prepared in yields up to 99%. The resultant polymers exhibited multiple stimuli-responsive behavior. The incorporated dynamic acetal moieties enabled the degradation of biomass-based PFEs under acidic conditions. Introducing the tetraphenylethylene (TPE) unit endowed the PFEs with attractive aggregation-induced emission (AIE) properties, enabling the sensitive detection of hydrazine. Thanks to the reaction of aldehydes and diamines, imino-PFEs with significant fluorescence changes according to acid–base variations were obtained and showed potential applications in logic gates, photopatterns and quadruple-mode secure information encoding. Thus, this work not only expands the scope of alkyne-based polymerizations, but also provides a new class of polyethers with versatile functions and applications.
在已有的基于炔烃的聚合方法中，活化内炔烃和苯酚的聚合还不发达。本文报道了一种简单的碳酸铯催化醛活化苯酚-炔咔嗒聚合反应，制备了各种重均分子量高达18060 g mol - 1的区域规则聚甲酰基醚（pfe），收率高达99%。所得聚合物表现出多重刺激响应行为。加入的动态缩醛部分使生物质基pfe在酸性条件下降解。引入四苯基乙烯（TPE）单元，使pfe具有吸引的聚集诱导发射（AIE）特性，从而实现了联氨的灵敏检测。由于醛和二胺的反应，获得了根据酸碱变化产生显著荧光变化的亚胺- pfe，并在逻辑门、光模式和四模安全信息编码中具有潜在的应用前景。因此，这项工作不仅扩大了炔基聚合的范围，而且提供了一类具有多种功能和应用的新型聚醚。
{"title":"Transition-metal-free click polymerization of aldehyde-activated internal diynes and diphenols toward stimulus-responsive multifunctional poly(formyl ether)s","authors":"Huifang Jia,Kun Jiang,Hongyi Suo,Xuling Wang,Baixue Li,Yusheng Qin,Ben Zhong Tang","doi":"10.1039/d6py00675b","DOIUrl":"https://doi.org/10.1039/d6py00675b","url":null,"abstract":"Among the well-established alkyne-based polymerization methodologies, the polymerization of activated-internal alkynes and phenols remains underdeveloped. Herein, a facile cesium carbonate catalyzed aldehyde-activated phenol-yne click polymerization was reported, and various regioregular poly(formyl ether)s (PFEs) with weight-average molecular weights up to 18 060 g mol−1 were prepared in yields up to 99%. The resultant polymers exhibited multiple stimuli-responsive behavior. The incorporated dynamic acetal moieties enabled the degradation of biomass-based PFEs under acidic conditions. Introducing the tetraphenylethylene (TPE) unit endowed the PFEs with attractive aggregation-induced emission (AIE) properties, enabling the sensitive detection of hydrazine. Thanks to the reaction of aldehydes and diamines, imino-PFEs with significant fluorescence changes according to acid–base variations were obtained and showed potential applications in logic gates, photopatterns and quadruple-mode secure information encoding. Thus, this work not only expands the scope of alkyne-based polymerizations, but also provides a new class of polyethers with versatile functions and applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Leanne M. Stafast,Jan M. Peschel,Johanna Schreiber,Christine Weber,Michael Gottschaldt,Ulrich S. Schubert
Suitably protected triflate and trifluorotosylate functionalized d-fructopoyranose and d-mannopyranose were studied as initiators for the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline. While triflates proved to be fast initiators, the fructose triflate suffered from low stability due to the ethylene glycol spacer on C1. Whereas the fructose trifluorotosylate showed fast initiation characteristics due to steric exposure of its leaving group, the mannose derivative was slow in initiating the CROP because of the attachment of the leaving group at C6 of the pyranose ring. Azide ω-end functionalized poly(2-ethyl-2-oxazoline)s (PEtOx) were accessible from both protected carbohydrate initiators leading to α-carbohydrate, ω-azide end functionalized building blocks after deprotection. These were applied in a strain-promoted azide alkyne cycloaddition with cyclooctyne end-functionalized polylactide. The resulting sugar-containing block copolymers might present suitable alternatives for PEGylated polyesters that are capable of targeting breast cancer cells due to their fructose moieties, or macrophages due to their mannose moieties, respectively.
{"title":"Fructose and mannose-based initiators for the synthesis of poly(2-ethyl-2-oxazoline) block copolymers","authors":"Leanne M. Stafast,Jan M. Peschel,Johanna Schreiber,Christine Weber,Michael Gottschaldt,Ulrich S. Schubert","doi":"10.1039/d6py00612d","DOIUrl":"https://doi.org/10.1039/d6py00612d","url":null,"abstract":"Suitably protected triflate and trifluorotosylate functionalized d-fructopoyranose and d-mannopyranose were studied as initiators for the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline. While triflates proved to be fast initiators, the fructose triflate suffered from low stability due to the ethylene glycol spacer on C1. Whereas the fructose trifluorotosylate showed fast initiation characteristics due to steric exposure of its leaving group, the mannose derivative was slow in initiating the CROP because of the attachment of the leaving group at C6 of the pyranose ring. Azide ω-end functionalized poly(2-ethyl-2-oxazoline)s (PEtOx) were accessible from both protected carbohydrate initiators leading to α-carbohydrate, ω-azide end functionalized building blocks after deprotection. These were applied in a strain-promoted azide alkyne cycloaddition with cyclooctyne end-functionalized polylactide. The resulting sugar-containing block copolymers might present suitable alternatives for PEGylated polyesters that are capable of targeting breast cancer cells due to their fructose moieties, or macrophages due to their mannose moieties, respectively.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiadong Lin,Qinghua Yang,Xingtao Wang,Lin Li,Bing Wu,Zixuan Li,Fenggang Liu
Organic electro-optic materials are regarded as core candidates for next-generation co-packaged optics and AI high-speed optical interconnection systems, yet their practical applications are hindered by the trade-off between electro-optic activity and thermal stability. In this work, a series of binary crosslinkable chromophores (LD1–LD4) was designed and synthesized using methoxyaniline derivatives as electron donors. Orthogonal crosslinking sites for the anthracene/maleimide Diels–Alder reaction and azide–alkyne Huisgen cycloaddition were introduced into the molecular framework, enabling the construction of rigid covalent networks. The resulting crosslinked thin films exhibit a high glass transition temperature of 148–152 °C and an electro-optic coefficient of 213–267 pm V−1. Long-term high-temperature aging tests demonstrate that the poled films maintain over 89.9% of their initial orientation after 500 h of operation at 85 °C. Compared with previously reported aniline- and tetrahydroquinoline-based binary crosslinking materials, the LD series achieves balanced high performance, simplified synthetic routes and reduced costs.
{"title":"Methoxyaniline-based binary crosslinkable chromophores for high-performance organic electro-optic thin films","authors":"Jiadong Lin,Qinghua Yang,Xingtao Wang,Lin Li,Bing Wu,Zixuan Li,Fenggang Liu","doi":"10.1039/d6py00764c","DOIUrl":"https://doi.org/10.1039/d6py00764c","url":null,"abstract":"Organic electro-optic materials are regarded as core candidates for next-generation co-packaged optics and AI high-speed optical interconnection systems, yet their practical applications are hindered by the trade-off between electro-optic activity and thermal stability. In this work, a series of binary crosslinkable chromophores (LD1–LD4) was designed and synthesized using methoxyaniline derivatives as electron donors. Orthogonal crosslinking sites for the anthracene/maleimide Diels–Alder reaction and azide–alkyne Huisgen cycloaddition were introduced into the molecular framework, enabling the construction of rigid covalent networks. The resulting crosslinked thin films exhibit a high glass transition temperature of 148–152 °C and an electro-optic coefficient of 213–267 pm V−1. Long-term high-temperature aging tests demonstrate that the poled films maintain over 89.9% of their initial orientation after 500 h of operation at 85 °C. Compared with previously reported aniline- and tetrahydroquinoline-based binary crosslinking materials, the LD series achieves balanced high performance, simplified synthetic routes and reduced costs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Research on polyester rings has primarily focused on six- to seven-membered cyclic monomers, while macrocyclic monomers remain largely unexplored. Therefore, ethylene brassylate (EB), a seventeen-membered biobased macrocyclic lactone costing less than $10 kg−1 was selected for this project. Linear poly(ethylene brassylate) (l-PEB) was synthesized using propargyl alcohol as the initiator and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst. Under optimized conditions l-PEBs with molecular weights (MWs) ranging from 1.4 to 17.5 kDa with dispersities between 1.27 and 1.53 were obtained, as determined by size exclusion chromatography (SEC). Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI MS) identified α-propargyl-ω-hydroxy-PEB as the major product, together with minor α-propargyl-ω-propargyl-PEB and α-hydroxy-ω-hydroxy-PEB byproducts. The major product was azidified to α-propargyl-ω-azido-PEB and subsequently cyclized by copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC). During azidification, the dihydroxy byproduct converted into a diazide derivative, while the dialkyne byproduct remained unreacted. CuAAC of the minor byproducts produced cyclic dimers, while combinations of all three linear precursors generated small amounts of higher-order cyclic polymers. Cyclic PEBs with molecular weights of 1400, 2000, 2500, and 4800 Da were successfully synthesized. The structures of the linear, azidified, and cyclic PEBs were confirmed by MALDI MS, SEC, nuclear magnetic resonance (NMR), and Fourier-transform infrared spectroscopy (FTIR).
{"title":"Fabrication of cyclic poly(ethylene brassylate) from ethylene brassylate: a cost-effective biobased seventeen-membered macrocyclic monomer","authors":"Mahi Ahmad,Aidee Hernandez,Scott M. Grayson","doi":"10.1039/d6py00480f","DOIUrl":"https://doi.org/10.1039/d6py00480f","url":null,"abstract":"Research on polyester rings has primarily focused on six- to seven-membered cyclic monomers, while macrocyclic monomers remain largely unexplored. Therefore, ethylene brassylate (EB), a seventeen-membered biobased macrocyclic lactone costing less than $10 kg−1 was selected for this project. Linear poly(ethylene brassylate) (l-PEB) was synthesized using propargyl alcohol as the initiator and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst. Under optimized conditions l-PEBs with molecular weights (MWs) ranging from 1.4 to 17.5 kDa with dispersities between 1.27 and 1.53 were obtained, as determined by size exclusion chromatography (SEC). Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI MS) identified α-propargyl-ω-hydroxy-PEB as the major product, together with minor α-propargyl-ω-propargyl-PEB and α-hydroxy-ω-hydroxy-PEB byproducts. The major product was azidified to α-propargyl-ω-azido-PEB and subsequently cyclized by copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC). During azidification, the dihydroxy byproduct converted into a diazide derivative, while the dialkyne byproduct remained unreacted. CuAAC of the minor byproducts produced cyclic dimers, while combinations of all three linear precursors generated small amounts of higher-order cyclic polymers. Cyclic PEBs with molecular weights of 1400, 2000, 2500, and 4800 Da were successfully synthesized. The structures of the linear, azidified, and cyclic PEBs were confirmed by MALDI MS, SEC, nuclear magnetic resonance (NMR), and Fourier-transform infrared spectroscopy (FTIR).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report a tandem HAT/XAT mechanism for the scission of poly(methyl methacrylate)-co-poly(methyl α-chloroacrylate) copolymers. Silyl radicals, generated from silanes via HAT, facilitate halogen abstraction from the polymer main chain and subsequent chain degradation. The kinetics and versatility were investigated using different photoinitiators, providing an efficient radical-mediated strategy for upcycling non-hydrolyzable polymers.
{"title":"A novel tandem photochemical route to PMMA copolymer degradation sequential HAT and XAT reactions involving silanes","authors":"Ozge Ozyildirim,Mina Kati,Huseyin Cem Kiliclar","doi":"10.1039/d6py00482b","DOIUrl":"https://doi.org/10.1039/d6py00482b","url":null,"abstract":"We report a tandem HAT/XAT mechanism for the scission of poly(methyl methacrylate)-co-poly(methyl α-chloroacrylate) copolymers. Silyl radicals, generated from silanes via HAT, facilitate halogen abstraction from the polymer main chain and subsequent chain degradation. The kinetics and versatility were investigated using different photoinitiators, providing an efficient radical-mediated strategy for upcycling non-hydrolyzable polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Molecular net gels (MN gels) are polymer gels constructed based on a topological structural design principle. The MN gels are prepared by penetrating polymerization of N-isopropylacrylamide (NIPAAm) in the presence of molecular nets (MNs), which are soluble ultra-high-molecular-weight three-dimensional network polymers. In this study, we investigated the mechanical properties of MN gels prepared with various MN concentrations that provide “cross-linking space”. The MN gels exhibited highly flexible mechanical properties, and as the MN concentration increased, the elastic modulus, fracture stress, and toughness increased, suggesting that MN could function as a “cross-linker”. Interestingly, even with an increase in MN concentration—i.e., an increase in elastic modulus—the fracture strain was almost constant. Furthermore, since MN gels are composed of temperature-responsive PNIPAAm, we investigated the temperature dependence of their mechanical properties. Above the lower critical solution temperature (LCST) of PNIPAAm, a significant increase in elastic modulus and fracture stress was observed compared to below the LCST, without accompanying large volume shrinkage. In addition, stress relaxation and plasticity of the MN gels were also investigated. The results revealed that the MN gels exhibit plastic behavior comparable to that of un-cross-linked polymers. These observations that the MN gels exhibit both elastic and plastic responses depending on the timescale of deformation are likely due to their dynamic cross-linking structure. Thus, the MN gels represent a novel class of gel materials with unprecedented properties.
{"title":"Properties of gels topologically cross-linked with physical restraints","authors":"Hiroaki Ogawa,Yusuke Taoka,Yuichi Ohya","doi":"10.1039/d6py00629a","DOIUrl":"https://doi.org/10.1039/d6py00629a","url":null,"abstract":"Molecular net gels (MN gels) are polymer gels constructed based on a topological structural design principle. The MN gels are prepared by penetrating polymerization of N-isopropylacrylamide (NIPAAm) in the presence of molecular nets (MNs), which are soluble ultra-high-molecular-weight three-dimensional network polymers. In this study, we investigated the mechanical properties of MN gels prepared with various MN concentrations that provide “cross-linking space”. The MN gels exhibited highly flexible mechanical properties, and as the MN concentration increased, the elastic modulus, fracture stress, and toughness increased, suggesting that MN could function as a “cross-linker”. Interestingly, even with an increase in MN concentration—i.e., an increase in elastic modulus—the fracture strain was almost constant. Furthermore, since MN gels are composed of temperature-responsive PNIPAAm, we investigated the temperature dependence of their mechanical properties. Above the lower critical solution temperature (LCST) of PNIPAAm, a significant increase in elastic modulus and fracture stress was observed compared to below the LCST, without accompanying large volume shrinkage. In addition, stress relaxation and plasticity of the MN gels were also investigated. The results revealed that the MN gels exhibit plastic behavior comparable to that of un-cross-linked polymers. These observations that the MN gels exhibit both elastic and plastic responses depending on the timescale of deformation are likely due to their dynamic cross-linking structure. Thus, the MN gels represent a novel class of gel materials with unprecedented properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"74 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lai Wei,Yuliang Gao,Kehong Lin,Xuhong Guo,Yiming Wang
Boron neutron capture therapy (BNCT) has emerged as a precise and safe radiotherapy technique for the treatment of cancers. To achieve ideal radiotherapy effects, the major hurdle lies in the enrichment of boron in cancer cells. Here, a strategy of organocatalysis-mediated intracellular growth of supramolecular polymers for the accumulation of boron in cancer cells is described. The involved organocatalyst can accelerate the intracellular formation and self-assembly of boron-containing monomers, generating boron-rich supramolecular polymers in cancer cells that lead to 2.4 times higher boron content than in the non-assembling case. This work would accelerate the exploitation of new boron delivery methods for high-efficiency BNCT.
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